Process for producing nitroso diazo solutions



Patented Oct. 4, 1932 Duran: STATES PATENT OFFICE RUDOLPH JUNG, orOFFENBAGH-ON-THE-MAIN, GERMANY, AssIeNon TO GENERAL ANILINE worms; 1nd,or new YORK, N. Y.,.A conroan'rron or DELAWARE rnocnss FOR PRODUCINGm'rnoso nIAzo SOLUTIONS in Drawing. Application filed -March8, 1929,Serial No. 345,598, and in Germany March 15, 1928.

My present invention relates toa process of producing nitrosodiazosolutions to be used for dyeing purposes, more particularly it relatesto a process of preparing solutions containing N-nitroso-diazoniumcompounds of the diphenylamine series.

Diazo compounds of the diphenylamine series yield valuable blue shadeswhen com- I tion of the diphenylamine'series an alakali bined on thefiber with 2.3-hydroxynaphthoyl-arylamides. It has been found that theN-nitroso-diazo compounds have a higher combining power than the simplediazo compounds free from nitroso groups, and therefore theN-nitrosodiazo compounds of the diphenylamine series are advantageouslyused for preparing the dyestuffs. The nltroso group is split oif fromthe complete dyestuffs by a suitable after-treatment of the dyedmaterial. I

In order to spare the dyer the manufacture of diazo compounds it iscustomary in the art to furnish him with-ready-made diazo preparations.But solid nitrosodiazo preparations of the diphenylamine series cannotbe produced on a technical scale as according tomy experiments thenitroso groups are split off during the drying process.

I have now found that nitroso diazo solutions of the diphenylamineseriescan be produced from soliddiazo preparations by add ing to asolution of a solid diazo preparanitrite and a substance setting freenitrous acidfrom the nitrite. The addition of this acid substance is notnecessary whenthe solid diazo preparation itself contains the sufiicientamount of an acid.

In order to further illustrate my invention the following examples aregiven, but I wish it to be understood that 'I am not limited to i theparticular products nor reaction conditions mentioned therein; the'partsare by weight: V

Example 1.A quantity of the acid diazonium sulfate ofpara-aminodiphenylamine corresponding to 184 parts of the base isdissolved in water. Then a solutionof 69 parts of sodium nitrite isadded while stirring. After a short time theN-nitroso-diphenylamine-t-diazonium salt is formed in the solution.

xEccample 2.A solution of the double salt of zinc chloride and4J-ethOX'y-diphenylaminel-diazoniumchloride corresponding to 228 partsof the base is mixed while stirring with a solution of 69'parts ofsodium nitrite and with 105 parts of hydrochloric acid of B. After ashort time the' N nitroso-d ethoxy-diphenylamine-t-diazonium salt isformed in'thesolution.

Example 3.A solution of U-methoxydiphenylamine-l-diazonium chloridecorresponding to 214: parts of vthe base is mixed while stirring with asolution of 69 parts of sodium nitrite and with a sol'utio'n'of 80 partsof oxalic acid. After'a short time the N- nitroso-U- methoxydiphenylamine fdiazonium salt is formed in the solution Example 4.Asolution of the benzene sulfonate of 4 methyl-diphenylaminA-diazoniumcorresponding to 198 parts of the base is mixed while stirring withasolution' of 69 parts of'sodiufn nitrite and with parts of glacialacetic acid. After a short time the N- ntr'oso 4- methdxy-diphenylamine4.} diazonium salt is formed in the solution. I

E wampze 5'.A solution'of the acid naphthalene 1.5 L disulfonate of 3'-m ethyl 4"- chlorodiphenylamine -L diazonium corresponding to 232,5parts ofthe'base are mixed while stirringiwith a solution of v69 p artsof sodium nitrite. "After a shortftime the N- nitroso 3"-methyl 4-ohlorodiphenylaminet-diazon'iumsalt is formed in the solution. Example6'.Asolution of thedoubl'e salt of zinc chlorideand 4:-chlorodiphenylamine- 4-di'azofiiumchloride corresponding to 218 parts ofthe base are mixed while stirring with a solution of 69 parts of sodiumnitrite and with 120 parts of sodium bisulfate.

, After ashort time the -nitroso-4c .-chlorodiphenylamine--diazoniumsalt is formed in the solution. r, I

5 i 1.. Theprocess of preparing nitroso-dlazo solutions to be used fordyeing purposes Which'comp rises dissolving in Water a solid diazopreparation of an amino-diphenylamr ine compound of'the general formula:

wherein X means hydrogen, halogen, an alkoxy or analkyl grou'p,;andadding "to this 7 solution substances capable of producing I nitrousacid. 7

-2. The processo'ff preparing nitroso-diaio" solutions to be use d .f ordyeing purposes which comprises dissolving in Water a solid.- diazopreparation of an,amino-diphenylamine compoundof the general formula:

wherein X means hydrogen, halogen, 'an I alkoXy-oran alkyl group, andadding to this 1 solution'an alkali'nitrite and a substance cav pable ofsetting 'freenitrous acid fronithe -3o,nitrite.' .7 V The process ofpreparing nitroso-diazo E solutions to beused for dyeing purposes r"which comprises dissolving in Water a solid diazo preparation of anamino-diphenylam inecompoundof the general formulaz vwherein X meanshydrogen, Cl,rthe methyl j 49 or an'alkoxy group, and addingtolthissolution an; alkaliynitrite'and a substance ca- I pable of setting freenitrous acidfrom the W nitrite.' I s fhtQThe processor preparing anitroso-diazo v solutionto be used $011 dyeing j purposes v whichcomprises dissolving in Water a solid diazoipreparationiof 4-amino-tmetl1oxydiphenylamineand adding to thissolutionjan i V alka1initrite anda substance-capablei-of set tingfree nitrous acid from the nitrite, r

; g 5. The process ofpreparing a nitroso-diazo solutionlto be used fordyeing purposes a V which comprises dissolving inwatera quanv I V t'ityfof f methox -diphenylamine 4 -vdia zo i weight ofthe base, mixing thissolution with t a solution .of;.6 9 part s by Weight-of sodium; nitrite,and'jtheii adding thereto a solutionof 180 partsby'weightlof oxalicacid; i

7 In testimony whereof, I aflixiny signature.

" niumc'hl'oride corresponding to214'parts'by f RUDOLPH JUNd;

